Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G

Definitions

• the present invention relates to a resin composition for a photocurable lining material, a photocurable lining material, and a cured product thereof.
• thermosetting rehabilitation method using a lining material using a styrene unsaturated polyester resin composition and a vinyl ester resin composition is often used. There is a need to shorten the construction time.
• the problem to be solved by the present invention is a resin composition for a photocurable lining material, which exhibits appropriate thickening behavior, is excellent in curability, and can obtain a cured lining material having excellent bending strength, tensile elongation, and heat resistance. To provide things.
• the present inventors have found that a resin composition for a photocurable lining material containing a specific resin component, a thickener and a photopolymerization initiator can solve the above-mentioned problems, and have completed the present invention.
• the present invention relates to a resin composition for a photocurable lining material, which comprises.
• the photocurable lining material obtained from the resin composition for a photocurable lining material of the present invention has excellent curability, and a cured lining material having excellent bending strength, tensile elongation, and heat resistance can be obtained. It can be suitably used for pipe rehabilitation of pipes and the like. It can also be used for infrastructure repair applications such as water pipes and other gas pipes and electric power pipes, and for repair prepregs such as bathroom waterproof floors.
• the resin composition for a photocurable lining material of the present invention comprises a resin component (A) containing an epoxy (meth) acrylate (a1) having a carboxyl group and an unsaturated monomer (a2) as essential components, and a thickener. It contains (B) and a photopolymerization initiator (C).
• (meth) acrylate means one or both of acrylate and methacrylate
• (meth) acrylic acid means one or both of acrylic acid and methacrylic acid
• the epoxy (meth) acrylate (a1) having a carboxyl group can be obtained, for example, by an ester reaction between an epoxy (meth) acrylate and a dibasic acid, but since the curability is further improved, the dibasic acid can be used as the dibasic acid. Unsaturated dibasic acid is preferable, and maleic anhydride is more preferable.
• dibasic acid examples include unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic acid anhydride; phthalic acid, phthalic acid anhydride, phthalic acid anhydride, isophthalic acid, and terephthalic acid.
• the epoxy (meth) acrylate can be obtained, for example, by reacting an epoxy resin with (meth) acrylic acid.
• epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like.
• the reaction between the epoxy resin and (meth) acrylic acid described above is preferably carried out at 60 to 140 ° C. using an esterification catalyst. Further, a polymerization inhibitor or the like can also be used.
• the molar ratio (OH / COOH) of the hydroxyl group to the carboxyl group in the epoxy (meth) acrylate (a1) having a carboxyl group is 95/5 to 50/50 because it exhibits more appropriate thickening behavior. It is preferable, 90/10 to 60/40 is more preferable.
• the acid value of the epoxy (meth) acrylate (a1) having a carboxyl group is preferably 10 to 50, more preferably 15 to 40, because a more appropriate thickening behavior can be obtained.
• Examples of the unsaturated monomer (a2) include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate alkyl ether, and polypropylene glycol (meth) acrylate.
• Examples thereof include polyfunctional (meth) acrylate compounds such as erythritol hexa (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, diallylphthalate, and divinylbenzene, and among these, copolymerization with the resin component (A). It is preferable to contain a polyfunctional (meth) acrylate compound because it has excellent properties and can further improve curability, bending strength, tensile elongation, and heat resistance. These unsaturated monomers may be used alone or in combination of two or more.
• the mass ratio (a1 / a2) of the radical curable resin (a1) and the unsaturated monomer (a2) is 25 / because the balance between the resin impregnation property into the fiber and the curability is further improved.
• the range of 75 to 75/25 is preferable, and the range of 30/70 to 70/30 is more preferable.
• the refractive index of the resin component (A) is preferably in the range of 1.530 to 1.550 because the curability is further improved.
• the resin component (A) contains the epoxy (meth) acrylate (a1) and the unsaturated monomer (a2) as essential components, but may contain other resin components.
• thickener (B) examples include metal oxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, metal hydroxides, isocyanate compounds, and thermoplastic powder resins.
• metal oxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, metal hydroxides, isocyanate compounds, and thermoplastic powder resins.
• Magnesium oxide is preferred because it provides proper viscosity behavior.
• These thickeners may be used alone or in combination of two or more. Further, in order to improve the thickening behavior, a thickening aid such as a quaternary ammonium salt may be used in combination with magnesium oxide which is a thickening agent.
• the amount of the thickener (B) used is preferably in the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the resin component (A), since more appropriate viscosity behavior can be obtained.
• the range of 5 to 10 parts by mass is more preferable.
• Examples of the photopolymerization initiator (C) include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2.
• Anthracinone compounds such as (also known as Mineral's Ketone), 4,4'-diethylaminobenzophenone, ⁇ -acyloxime ester, benzyl, methylbenzoylformate ("Biacure 55"), 2-ethylanthraquinone; 2,4.
• Acylphosphine oxide compounds such as 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphinoxide; 3,3', 4,4'-tetra (tert-butyloperoxycarbonyl) benzophenone , Acrylicized benzophenone and the like can be used.
• these photopolymerization initiators (C) can be used alone or in combination of two or more.
• the amount of the photopolymerization initiator (C) used is excellent in curability, it is preferably in the range of 0.1 to 3 parts by mass, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the resin component (A). The range of parts by mass is more preferable.
• the resin composition for a photocurable lining material of the present invention contains a resin component (A), a thickener (B), and a photopolymerization initiator (C), but other additions are necessary as necessary. It may contain an agent.
• Examples of the other additives include polymerization inhibitors, antioxidants, photostabilizers, solvents, defoamers, thixo-imparting agents, leveling agents, tackifiers, antistatic agents, flame retardants, and curing accelerators.
• Examples include pigments, fillers, reinforcing materials, aggregates and the like.
• the photocurable lining material of the present invention contains the resin composition for the photocurable lining material and the glass fiber reinforcing material.
• the form of the glass fiber reinforcing material for example, a chopped strand mat made of plain weave and chopped strands cut into 2 inches are randomly oriented and fixed with a binder to form a non-woven fabric, and chopped strand mats and rovings are placed in the same direction. Alignment, unidirectional sheet integrated with auxiliary weft thread and binder, multi-axis stitch base material integrated with stitch thread by laminating the above unidirectionally aligned sheet in multiple directions, unidirectional alignment A tubular or mat-shaped material such as a stitch mat in which a sheet material and chopped strands randomly oriented are integrated by stitching is used. Further, these glass fiber reinforcing materials may be used alone or in combination of two or more.
• glass fiber for example, those obtained by using alkali-containing glass (C glass), low-alkali glass, non-alkali glass (E glass) or the like as raw materials can be used, but mechanically in infrastructure repair applications. It is preferable to use acid resistant glass (ECR glass) having excellent properties and corrosion resistance.
• C glass alkali-containing glass
• E glass non-alkali glass
• ECR glass acid resistant glass
• the content of the glass fiber reinforcing material in the photocurable lining material of the present invention is preferably in the range of 30 to 60% by mass because the mechanical properties are further improved.
• a method of directly laminating and impregnating the photocurable lining resin composition of the present invention and a glass fiber reinforcing material on a repair surface such as concrete to form a lining material layer or in advance.
• the film on the adherend surface is peeled off as necessary at the repair site. According to the shape of the repaired part, it is hardened by pressure crimping with a roller or the like and irradiation with light.
• Examples of the method for curing the photocurable lining material of the present invention include a method of irradiating ionized radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays, and a specific energy source or
• Examples of the curing device include a sterilizing lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium-pressure or high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a fluorescent chemical lamp, and an LED lamp.
• Examples thereof include ultraviolet rays using natural light as a light source, or electron beams using a scanning type or curtain type electron beam accelerator.
• the photocurable lining material of the present invention is excellent in quick-curing property and thick film curing property, it can be suitably used for pipe rehabilitation such as sewer pipes. It can also be used for infrastructure repair applications such as water pipes and other gas pipes and electric power pipes, and for repair prepregs such as bathroom waterproof floors.
• the refractive index of the resin component was measured using a universal Abbe refractive index meter (“ER-7MW” manufactured by Elma Sales Co., Ltd.), the acid value was JIS-K-6901, and the epoxy equivalent was JIS-K-7236. Each was measured in accordance with it.
• ER-7MW Abbe refractive index meter
• the part was added, the reaction temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. After that, 0.7 parts by mass of 2-methylimidazole was further added, and the acid value and epoxy equivalent were measured. After confirming that the acid value was 7.0 or less and the epoxy equivalent was 5000 or more, the reaction was terminated. After cooling to around 40 ° C., 0.05 part by mass of t-butyl hydroquinone and 300 parts by mass of phenoxyethyl methacrylate were added and dissolved. After stirring for 10 minutes, 75.4 parts by mass of maleic anhydride was added, the temperature was raised to 90 ° C., and the reaction was carried out for 5 hours.
• the part was added, the reaction temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. After that, 0.7 parts by mass of 2-methylimidazole was further added, and the acid value and epoxy equivalent were measured. After confirming that the acid value was 7.0 or less and the epoxy equivalent was 5000 or more, the reaction was terminated. After cooling to around 50 ° C., 0.05 part by mass of t-butylhydroquinone was added, and the mixture was taken out from the reaction vessel to obtain an epoxy (meth) acrylate (Ra1-1). The acid value was 3.0.
• Example 1 Production of resin composition (1) for photocurable lining material
• Phenylphosphine oxide (hereinafter abbreviated as "photopolymerization initiator (C-1)") 1.5 parts by mass, thickener ("Magmicron MD504-2” manufactured by Gokoku Dye Co., Ltd .; hereinafter, “thickening agent” Agent (B-1) ”is abbreviated.) 3.0 parts by mass was mixed to obtain a resin composition (1) for a photocurable lining material.
• the refractive index of the resin component (A-1) composed of epoxy (meth) clearate (a1-1), phenoxyethyl methacrylate, and diethylene glycol dimethacrylate was 1.530.
• Example 2 Production and evaluation of resin composition (2) for photocurable lining material
• 40 parts by mass of epoxy (meth) clearate (a1-2) having a carboxyl group 40 parts by mass of phenoxyethyl methacrylate, 20 parts by mass of trimethylolpropane trimethacrylate, photopolymerization initiator (C-1) obtained in Synthesis Example 2.
• 1.5 parts by mass and 2.0 parts by mass of the thickener (B-1) were mixed to obtain a resin composition (2) for a photocurable lining material.
• the refractive index of the resin component (A-2) composed of epoxy (meth) clearate (a1-1), phenoxyethyl methacrylate, and trimethylolpropane trimethacrylate was 1.530.
• the cured product obtained above was evaluated according to the following criteria by measuring the bending strength in accordance with JIS K7171-1. ⁇ : 100 MPa or more ⁇ : less than 100 MPa [tensile elongation rate] The cured product obtained above was subjected to a tensile test of a 1B test piece in accordance with JIS K7161-1 and 2, the tensile elongation was measured, and evaluated according to the following criteria. ⁇ : 2% or more ⁇ : less than 2% [heat resistance] Regarding the cured product obtained above, the deflection temperature under load was measured in accordance with JIS K7911-1, and the heat resistance was evaluated according to the following criteria. ⁇ : 85 ° C or higher ⁇ : Less than 85 ° C
• Table 1 shows the evaluation results of the resin compositions (1) to (2) and (R1) to (R2) for the photocurable lining material obtained above.
• the photocurable lining material obtained from the resin composition for the photocurable lining material of the present invention of Examples 1 and 2 is excellent in thickening behavior, and the cured product is excellent in bending strength, tensile elongation, and heat resistance. confirmed.
• Comparative Example 1 is an example in which an unsaturated polyester resin is used instead of the epoxy (meth) acrylate (a1) having a carboxyl group, but it has been confirmed that the bending strength and heat resistance are insufficient.
• Comparative Example 2 is an example in which an epoxy (meth) acrylate (a1) having no carboxyl group is used instead of the epoxy (meth) acrylate (a1) having a carboxyl group, but the viscosity increase is insufficient. Was confirmed.

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• 2021
  • 2021-09-09 WO PCT/JP2021/033080 patent/WO2022070816A1/ja not_active Ceased
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